Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/251—Mica
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/256—Heavy metal or aluminum or compound thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/256—Heavy metal or aluminum or compound thereof
  • Y10T428/257—Iron oxide or aluminum oxide
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

• the present invention relates to matte films made of a composition comprising a polyarylate resin, a polyester resin and a styrene resin or an acrylic resin, which are useful for matte films for drawings, leader tapes for magnetic tapes, labels, wall papers or synthetic papers.
• matte-finishing or roughening a film surface it is common to employ a so-called sand blasting method in which hard sand particles, etc. are blown to the film surface to roughen it, a coating method wherein a resin containing inorganic particles, etc. is coated on a film surface, a method wherein inorganic particles such as Si0 2 or TiO 2 particles are preliminarily incorporated into the resin for the film, or a chemical etching method in which the film surface is eroded by an acid or solvent.
• the matte-finishing of polyester films is most commonly carried out by the sand blasting method or the coating method.
• a study is being made to obtain a matte finish surface by an addition of an organic synthetic resin.
• Japanese Examined Patent Publication No. 12368/1980 discloses a combination of a linear polyester resin with a polycarbonate and at least two other polymers
• Japanese Examined Patent Publication No. 28096/1983 discloses a combination of a linear polyester resin with a phenoxy resin
• Japanese Examined Patent Publication No. 28097/1983 discloses a combination of a linear polyester resin with a polyarylate resin.
• Japanese Examined Patent Publication No. 2016/1974 discloses a process for producing a pearl-like film by incorporating a polystyrene to a polyester.
• the disclosed process is different from the present invention in the construction, object and effects.
• the present invention provides a matte film made of a composition
• a matte film made of a composition
• a composition comprising (a) from 3 to 20 parts by weight of a polyarylate resin made of terephthalic acid, isophthalic acid (the molar ratio of the terephthalic acid group to the isophthalic acid group being from 9 : 1 to 1 : 9) and a bivalent phenolic compound, (b) from 60 to 94 parts by weight of a linear polyester resin and (c) from 3 to 30 parts by weight of a styrene resin or an acrylic resin, and satisfying the following condition: where A is the parts by weight of the polyarylate resin and S is the parts by weight of the styrene resin or acrylic resin, and said film being stretched at least 1.5 times in at least one direction.
• the polyarylate resin used in the present invention is a copolymer polyester made of terephthalic acid, isophthalic acid and a bisphenol.
• a method for its preparation there may be mentioned a method in which dichlorides of terephthalic acid and isophthalic acid dissolved in a water-insoluble organic solvent are polymerized with a bisphenol dissolved in an aqueous alkaline solution by interfacial polymerization, a method in which dichlorides of terephthalic acid-and isophthalic acid are polymerized with a bisphenol in an organic solvent, a method in which terephthalic acid, isophthalic acid and a bisphenol are subjected to heat-melt polymerization in the presence of acetic anhydride, a method in which phenylesters of terephthalic acid and isophthalic acid and a bisphenol are subjected to heat-melt polymerization, or a method in which terephthalic acid and isophthalic acid and
• the matte finish and antistatic properties by introducing from 1 to 50 mol eq/ton of acid anhydride groups in the molecular chain of the polyarylate resin.
• the improvement in the matte finish is believed to be attributable to the fact that the acid anhydride groups hinder the compatibility with the linear polyester.
• the improvement of the antistatic properties is believed to be attributable to the fact that the copolymer polyarylate resin having acid anhydride groups is charged positively, while the linear polyester resin is charged negatively, and by the proper combination and arrangement of such two different types of resins, the positive and negative charges cancel out each other to present apparent antistatic properties. From the study of the electric charge in the case of such a combination, it has been found that the quantity of the electric charge varies depending upon the ratio of the copolymer polyarylate to the linear polyester resin and the state of the blend thereof.
• the state of the blend varies depending upon the amount of acid anhydride groups in the polyarylate, and as shown in the examples, it has been found that the electric charge remarkably decreases when the amount of the acid anhydride groups is within a proper range of from 1 to 50 mol eq/ton.
• the present inventors have conducted extensive researches to obtain such a proper condition constantly, and have found that good results can be obtained by melt-mixing under the following conditions.
• a matte film having improved antistatic properties can be obtained by incorporating from 0.001 to 5% by weight, based on the above-mentioned composition., of a phosphorus compound having the formula:
• the phosphorus compound is not limited to these preferred exmaples.
• the quantity of acid anhydride groups can be measured by the peak value of the infrared absorption spectrum at 1820 and 1760 cm -1 .
• the frictional static charge in the present invention is the electric charge caused by friction of a film with itself by means of Kyodai Kaken Model Rotary Static Tester at 20°C under a relative humidity of 40%. If the value exceeds 1000V, troubles attributable to the electric charge are likely to be caused, such being undesirable from the practical point of view.
• the linear polyester resin in the present invention is a polycondensation product of an acid component such as terephthalic acid, isophthalic acid or paraoxybenzoic acid with a diol component such as ethylene glycol or tetramethylene glycol, or it may be a mixture of at least two different kinds.
• an acid component such as terephthalic acid, isophthalic acid or paraoxybenzoic acid
• a diol component such as ethylene glycol or tetramethylene glycol
• polyethylene terephthalate and polybutylene terephthalate, which are satisfactory from the viewpoints of both the properties and costs.
• cross-linking agent or to provide crosslinkable branches, and to conduct cross-linking by heat, light or radiation prior to or after the stretching.
• the styrene resin in the present invention is a resin containing at least 50 mol % of a styrene group in the molecular chain.
• a polystyrene resin an acrylonitrile-styrene copolymer resin, an acrylonitrile-butadiene-styrene copolymer resin, a styrene-butadiene copolymer resin, a styrene-methylmethacrylate resin, or a mixture thereof.
• the styrene resin is not restricted to these specific examples.
• the acrylic resin in the present invention is a resin containing at least 50 mol % of an acrylate or methacrylate in the molecular chain.
• an acrylate or methacrylate in the molecular chain For instance, there may be mentioned a methyl methacrylate resin, an ethyl methacrylate resin, a butyl methacrylate resin, or a mixture thereof.
• the acrylic resin is not restricted to these specific examples.
• the suitable ranges are such that the polyarylate resin is from 3 to 20 parts by weight, preferably from 5 to 15 parts by weight, the linear polyester resin is from 60 to 94 parts by weight, preferably from 70 to 90 parts by weight, and the styrene resin or the acrylic resin is from 3 to 30 parts by weight, preferably from 5 to 20 parts by weight. If the ratio of the polyarylate resin to the styrene resin or acrylic resin is unbalanced to a large extent, it is difficult to obtain a uniform matte surface, or the mechanical properties will be inadequate.
• the styrene resin or the acrylic resin forms fine irregularities on the film surface and thus serves to fill the spaces between rough irregularties formed by the polyarylate resin, whereby it is possible to obtain a matte film having overall uniform irregularities. If the polyarylate resin is used alone, only a film having large irregularities is obtainable, which has a drawback that when used as a matte film for drawings, the writability is poor. Whereas, according to the present invention, the styrene resin or the acrylic resin precipitates as smaller particles than the polyarylate resin, and a film having a uniform matte surface properties is obtainable.
• the acrylic resin has a refractive index which is substantially different from other resins, and thus has an effect for whitening, whereby the resulting film looks as white as a paper.
• the mechanical properties can be improved by the incorporation of the styrene resin or the acrylic resin. This is considered attributable to the function of the styrene resin or the acrylic resin as a binder for the polyarylate resin and the linear polyester resin.
• the amount of the styrene resin or the acrylic resin is within the range to satisfy the above-mentioned formula. If the amount is outside the range, the above-mentioned synergistic effects can not be obtained, and no practically useful film will be obtained.
• inorganic additives such as TiO 2 or SiO 2 may be incorporated in the film of the present invention.
• the amount of an inorganic additive is preferably within a range of from 0.3 to 7 parts by weight. If the amount is less than this range, no adequate effect of the incorporation will be obtained. On the other hand, if the amount exceeds 7 parts by weight, there will be no substantial difference from the conventional inorganic-type matte films, and the features of the present invention will be lost. Besides, the transparency will be poor.
• the average particle size of the inorganic particles is preferably within a range of from 0.01 to 30 ⁇ m.
• the inorganic particles are preferably made of SiO 2 , TiO 2 , CaCO 3 , BaSO 4 , Ba 2 TiO 4 , A1203, kaolin, mica or talc.
• the material of the inorganic particles is not restricted to these specific examples. These inorganic particles are harder than the organic resins, and thus serves to improve the writing properties, particularly the writing properties by a hard pencil having a hardness of at least 3 H .
• the compound of the present invention has a relatively smooth surface in a non-stretched state. When stretched, however, irregularities will form.
• the stretching rate is at least 1.5 times, preferably at least 2 times, in at least one direction, when the resulting film is to be used as a matte film. It is possible to obtain a better film by biaxial stretching in both the longitudinal and transverse direction. In this case, it is also preferred that the biaxial stretching is conducted at a stretching rate of at least 1.5 times in each direction.
• the film of the present invention may be of a single layer structure. However, it may be made to have a multi layer structure in order to obtain higher strength or to attain lower costs. Namely, a layer of the compound of the present invention may be formed on one side or each side of a linear polyester resin film, which is then stretched at least 1.5 times in at least one direction. In this case, the mechanical properties are maintained by the linear polyester layer, and yet the product is inexpensive since the compound of the present invention is used only for the surface layer. Further, since the matte surface is provided only on the required side, the transparency can be improved over the single layer film.
• the film is stretched preferably at a temperature higher than the usual stretching temperature for a linear polyester resin film to obtain a good matte surface. More specifically, the stretching temperature is preferably from 90 to 125°C.
• the matte film of the present invention When the matte film of the present invention is used as a shrink film, no heat-setting is conducted after the stretching operation. Whereas, when the film is to be used for an application where the dimensional stability is required as in the case of a film for drawings, the heat-setting is necessary.
• the heat-setting temperature is preferably within a range of from 60°C below the melting point of the linear polyester resin to the melting point of the linear polyester resin.
• a polyarylate resin was prepared by the interfacial polymerization of a methylene chloride solution of mixed acid chlorides, i.e. terephthalic acid dichloride/ isophthalic acid dichloride at a ratio of 5 : 5, with bisphenol A dissolved in an aqueous alkaline solution.
• the polyarylate resin, a polyethylene terephthalate resin and a polystyrene resin were mixed in various ratios, and the mixture was heated, mixed and formed into chips by a double-screw extruder. Then, the chips were melted at 280°C by a 50 mm extruder and extruded from a T-die to obtain a film having a thickness of about 150 um.
• the film was monoaxially stretched 2 times at 90 0 by a double-roll type monoaxial stretching machine. The writing properties of the stretched film were evaluated. The results are shown in Table 1.
• a non-stretched film of a three component composition was prepared in the same manner as in Example 4 except that the polystyrene resin was replaced by a copolymer resin of acrylonitrile and styrene at a molar ratio of 4 : 6.
• the film was simultaneously biaxially stretched at 100°C at a longitudinal-transverse stretching rate of 3.3 x 3.3 times by a test stretching machine, and heat-set at 230°C.
• the biaxially stretched film thereby obtained was tested for the writing properties, the erasure and rewriting properties and the reproducibility, whereby good results were obtained with both a pencil and an ink. Further, the mechanical properties of the film were satisfactory as shown in Table 2.
• a non-stretched film comprising a center polyethylene terephthalate layer of 300 ⁇ m and a mixed resin layer of 100 um having the same composition as in Example 4 on each side of the polyethylene terephthalate layer, was prepared.
• This non-stretched film was stretched 3.3 times in the longitudinal direction at 90°C by a roll type longitudinal stretching machine and then 3.4 times in the transverse direciton at 100°C by a tenter-type stretching machine, and then immediately heat-set at 230°C.
• the stretched film had a large surface roughness as shown in Table 3 and good writing properties. Further, the mechanical properties were good as shown in Table 3.
• a polyarylate resin was prepared by the interfacial polymerization of a methylene chloride solution of mixed acid chlorides i.e. terephthalic acid dichloride/ isophthalic acid dichloride at a ratio of 5 : 5, with bisphenol A dissolved in an aqueous alkaline solution.
• the polyarylate resin, a polyethylene terephthalate resin and a polymethyl methacrylate resin were mixed in various ratios, and the mixture was heated, mixed and formed into chips by a double-screw extruder. Then, the chips were melted at 280°C by a 50 mm extruder, and extruded from a T-die to obtain a film having a thickness of about 500 pm.
• the film was monoaxially stretched 2 times at 95°C by a two-roll type monoaxial stretching machine. The stretched film thereby obtained was tested for the writing properties. The results are shown in Table 4.
• Anon-stretched film of a three component composition was prepared in the same manner as in Example 14.
• the film was simultaneously biaxially stretched at 100°C at a longitudinal-transverse stretching rate of 3.3 x 3.3 times by a test stretching machine, and heat-set at 230°C.
• the biaxially stretched film thereby obtained was tested for the writing properties, the erasure and rewriting properties and the reproducibility, whereby good results were obtained with both a pencil and an ink. Further, the mechanical properties of the film were satisfactory as shown in Table 5.
• a non-stretched film comprising a center polyethylene terephthalate layer of 300 ⁇ m and a mixed resin layer of 100 ⁇ m having the same composition as in Example 14 on each side of the polyethylene terephthalate layer, was prepared.
• This non-stretched film was stretched 3.3 times in the longitudinal direction at 90°C by a roll type longitudinal stretching machine and then 3.4 times in the transverse direciton at 100°C by a tenter-type stretching machine, and then immediately heat-set at 230°C.
• the stretched film had a large surface roughness as shown in Table 6 and good writing properties. Further, the mechanical properties were good as shown in Table 6.
• a polyarylate resin was prepared by the interfacial polymerization of a methylene chloride solution of mixed acid chlorides, i.e. terephthalic acid dichloride/ isophthalic acid dichloride at a ratio of 5 : 5, with bisphenol A dissolved in an aqueous alkaline solution.
• the polyarylate resin, a polymethyl methacrylate resin, a polyethylene terephthalate resin and a silica powder having an average particle size of 4pm were mixed in various ratios, and the mixture was heated, mixed and formed into chips by a double-screw extruder. Then, these chips were melted at 280°C by a 60 mm extruder, and extruded from a T-die.
• the film had a thickness of 500 ⁇ m.
• the non-stretched film was stretched 3.0 times in the longitudinal direction at 90°C by a roll-type longitudinal stretching machine, and then 3.4 times in the transverse direction at 100°C by a tenter method.
• the film hardness is improved by the addition of silica, whereby the writing properties particularly with a hard pencil having a hardness of at least 3H were improved remarkably.
• the non-stretched laminated film as used in Example 22 was stretched 3.3 times in the longitudinal direction at 100°C by a roll-type longitudinal stretching machine, and then 3.5 times in the transverse direction at 100°C by a tenter-type transverse stretching machine, and immediately heat-set at 230°C.
• the biaxially stretched film thus obtained was tested for the writing properties, the erasure and rewriting properties and the reproducibility. As shown in Table 8, good results were obtained with both a pencil and an ink. Further, the mechanical properties of the film were good as shown in Table 9.
• a copolymerized polyarylate containing a different number of acid anhydride groups was prepared by the interfacial polymerization of a methylene chloride solution of mixed acid chlorides, i.e. terephthalic acid dichloride/isophthalic acid dichloride at a ratio of 5 : 5, with bisphenol A dissolved in an aqueous alkaline solution having a different alkali concentration.
• the copolymerized polyarylate, polyethylene terephthalate and polymethyl methacrylate were mixed in various ratios, and the mixture was heated, mixed and formed into chips by a double-screw extruder.
• Example 30 The copolymerized polyarylate as used in Example 30, polyethylene terephthalate and polymethyl methacrylate were blended. To this mixture, a phosphorus compound having the formula: was added, and then heated, melted and chiped by a double-screw extruder. Then, these chips were melted at 280°C by a 50 mm extruder, and extruded from T-die to obtain a film having a thickness of 150 ⁇ m. The film was biaxially stretched at a longitudinal-transverse stretching rate of 3 x 3 times. Then, the frictional static charge caused by the frictional engagement of the film itself was measured at 20°C under a relative humidity of 40% by means of Kyodai Kaken Model Rotary Static Tester. The results are shown in Table 11.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Applications Claiming Priority (4)

Publications (2)

Family

ID=26513632

Family Applications (1)

Country Status (3)

Cited By (2)

Families Citing this family (1)

Citations (5)

Family Cites Families (2)

• 1985
  • 1985-11-11 EP EP19850114324 patent/EP0184028B1/de not_active Expired
  • 1985-11-11 DE DE8585114324T patent/DE3569258D1/de not_active Expired
  • 1985-11-20 US US06/800,157 patent/US4668569A/en not_active Expired - Fee Related

Patent Citations (5)

Also Published As

Similar Documents

Legal Events